Vinyl chloride resins plasticized with esters of phenyl phenoxy acetic acid



Patented July 15, 1952 UNITED .srATEs 11;

VINYL CHLORIDE RESINS l lili'srrciziab WITH ESTERS F P ENYr; BHENOXYW;

ACETIC ACID Joachim Dazzi, Dayton, 0

santo Chemical Company S tLLouis M0,, a cor; poration ofDelaware No Drawing "'ApplicationJune 24,1949,

hi0, assignor to Mon- Serial No. 101554913 This invention relates to new resinous compositions having'utility overwidely varying conditions. More particularly the invention relates to the use of esters of phenylphenoxyacetic acid as plasticizersfor vinyl chloride resins.

The primary purpose of thisinvention is to pro- I vide improved plasticizers for vinyl chloride resins.

Claims. (crfz cogacsy'f A further purpose of this invention is to provide new resinous compositions having desirable flexibility over wide temperature ranges. A still further purposeof this; invention is to provide inexpensiveresinous compositions which retain their plastic properties after subjection toelevated'temperaturesand long periods of time; o It has'been found that'esters of phenylph'enox y acetic acid having the following structural formula are efficient plasticizers for vinyl chloride polymers wherein R is an aliphatic radical of the group 7 consisting of hydrocarbon, thiahydrocarbon and oxahydrocarbon radicals having atotal of from four-to twelve carbon, oxygen and sulfur atoms. Thenewplasticizers-may be esters of the orthometa, and para-phenylphenoxyacetic acids and v various aliphatic alcohols, such as n-butyl alcohol,

t-butanol, n-hxanol, the amylalcohols, 2-ethylhexyl alcohol, 'thenonyl alcohols and other alipha'tic straight and branched chain alcohols having up 'tOf twelve carbon atoms, theoxahyd iocarbon alcohols; such asv ethyl cellosolve' butyl cellos"olve, 2 -e thylhexoxyethyl alcohol; carbitol (diethylene glycol ethyl ether), butyl carbltol and other aliphatic alcoholsin whichgroups havebeen replaced by either oxygen atoms, the hief-a coh ls .su h a h a n-r nt lt3 ;6- lia cty coho and other. aliphatic alcohe fi h r in: one or more H2 groups have been, re,- placed by divalent sulfur atoms. In, all casesv Te R-IQQ Q lJ'LSWmHStQhaliejajtfital of from row to twelve carbon, oxygen and sulfur atoms the meme p p j The. following specific compounds are, included withinthescopeof.theclaimsv.

} for; polyvinyl lchlori'ole and copolymers of more than. 70 percent of vinyl chloride and" upto"'30 percent; of other monomers copolymerized there with; for/example vinyl acetate-and other vinyl esters. of monocarboxylic acids, "ethylmale'ate, ethyl. fumarate and: other alkyl esters of maleic and fumaricacids. .I1 I r The plasticizers are blended with the vinyl resin in the conventional manner, for example by mixing on a roll mil-l, a Banbury type mixer or any other-suitable. mixing device-.5; The plasti- QiZers aroused inproportions necessary to achieve the, esired plasticity. Although .the quantity of 1 1' plast cizer; will depend upon theparticular polye mer to be plasticized, itis generallyfo'und'that from 5 to percent of plasticizer will in most cases produce a satisfactory composition for general utility. Such quantity 10L plasticizer; will gfineltally remain as apermanent part oft-he. vinyl chloride polymers.

resin and the modified vinyl resin so prepared will not deteriorate Or become embrittled by reason of the loss of the plasticizer during use.

The value of the plasticizers are estimated by three tests: (1) compatibility, (2) volatility, and (3) Clash-Berg flex temperature. The compatibility is determined by visual inspection, clarity being a requisite in many applications for vinyl The volatility is estimated by the test of heating at 105 C. for 24 hours and measuring the percentage of the plasticizers evaporated by loss of weight. The Clash-Berg flex temperature is determined bycooling the polymer sample to about 50 C. and observing the change in the modulus of rigidity as the sample warms up to room temperature, the flex- .1

temperature being that at which the modulusof rigidity is 135,000 pounds per square inch. Of i 7 Example2 these tests the compatibility is of primary 'importance while the others are only critical for I certain applications. If the polymer is to be sub- Jected to outside Weather conditions flex tempera- I 'tures of 20 to -30 C. are desirable, otherwise 0 C. is satisfactory. If the polymer is to be subjected to elevated temperatures a volatilityof less than ten percent is advantageous, otherwise volatilities as high as percent are oftennotbb jectionable. The volatilities and flex temperatures, of polymer plasticizer blends are diflicult to predict and often have no apparent relationship to the physical constants ofuthe plasticizer.

The new plasticizers are of general utility in Y Example 4. ........:::::I

place of 2-ethy1hexano1. The resulting product was identified as 2-ethylhexoxyethyl p-phenyl-- phenoxyacetic acid.

Example 5 tested by means of the Clash-Berg flex temperature procedure and their volatility determined by the above described method. The following table sets forth the observed data.

The Ester of C. by Weight Example 3- The invention is defined by the following claims.

softening vinyl chloride polymers and are efiective over a wide range of temperatures. They may be used as the only plasticizing component in a compounded vinyl chloride polymer or they may be used in conjunction with other plasticizers.

Specific examples of the practice of this invention are: 1

Example 1 A solution of 0.45 mole of p-hydroxy biphenyl and 0.45 mole of sodium hydroxide was prepared by dissolving in 200 ml. of ethanol. f The I solution was added gradually to asolution or 0.6 mole of chloracetic acid and 0.3 mole of sodium carbonate in 120 ml. of water over a period of twenty-sevenminutes. The mixture was stirred atj'room temperature overnight and thenheated 7060 .to 70 C. for one hour. The solution was then acidified and the solid product which precipitated was identified as j p-phenylphenoxyacetic acid. I

" j Example 2 1 The acid prepared in accordance with the preceding example was mixed with a ten percent excess; of 2-ethylhexanol and heated in a benzene solution with a small proportion d p-toluenesulfonic acid. The water of reaction was removed from the reaction mixture as the benzene-water azeotrope, from which the Water was separatedby means of a Dean and Stark trap. The resulting product was identified as the 2-.ethylhexyl ester of p-phenylphenoxyacetic acid. J

v V rambles The procedure of the preceding example was repeated, except that 2-n-butoxy -ethyl'- alcohol was used in place of the 2-ethylhexanol. The product was identified as 2-n-butoxyethyl' pphenylphenoxyacetic acid. 1

The procedure of Example 2 was repeated cept' that 2-ethylhexoxyethyl alcohol was used in another. *polymerizable monomer comprises a polymer of at least 70 percent by weight of vinyl chloride and up to 30 percent of compatible therewith, and a compound having the structural formula:

wherein R is an aliphatic radical of the group con sisting of hydrocarbon, thiahydrocarbon andoxahydrocarbon radicals having a total o'f'from four totwelve carbon, oxygen and sulfur atoms. v

2. A resinous 1 composition, which comprises polyvinyl'chloride and from 5 .to GOpercent'by weightof an alkyl phenylphenoxyacetate, whereinfthe alkyl group has from four to twelve car bon atoms; v

3. A resinous composition which comprises polyvinyl chloride and from 5 to 60 percent by weight of an oxaalkyl phenylphenoxyacetate, wherein the oxaalkyl group has a total of from four to twelve oxygen and carbon atoms. [4. A resinous composition which comprises polyvinyl chloride and from 5 to 60 percent by weight of a thiaalkyl phenylphenoxyacetate, wherein the thiaalkyl group has from fourto twelve carbon and sulfur atoms.

5. A resinous composition comprising poly.- vinylchloride andfrom 5 to 60 percent by weight of 2-ethylhexyl p-phenylphenoxyacetate. 6-. A resinous composition comprising polyvinyl chloride and from 5 to 60 percent by weight ofbutoxyethyl'p-phenylphenoxyacetate. W b 7. A resinous composition comprising polyvinyl chloride and from 5. to 60 percent bywfi ghtwof 2-ethylhexoxyethyl p-phenylphenoxyacetate.

8. A resinouscompositionof matter, which comprisesa polymer of at least 70 percentby weight of vin'yl chloride and up. to 30 percent'of another. 'j pol yme'rizable monomer compatible therewith, and from .5 to 60 per cent by weight of the polymer of an {alkyl phenylphenoxyacetatp a wherein the alkyl group has from four to'twelv carbon atoms. 1. l.

9. A resinous composition ,of matter,f'wliich comprises a polymer of atleast 70 per' cent "by weight of vinyl chloride andup to 30 per cent 'of Volatility Per Cent 1 belles oww another polymerizable monomer compatible UNITED STATES PATENTS therewith, and from 5 to 60 per cent by weight of Number Name Date the polymer of an oxaalkyl phenylphenoxyacetate 2 170 995 Grether et a1 Aug. 29 1939 wherein the oxaalkyl group has from four to 2170996 Grether et 1939 twelve oxygen and carbon atoms. 5 2369985 safiord Feb 1945 10. A resinous composition of matter, which 2393495 Tam 1946 comprises a polymer of at least '70 per cent by 2396513 Jones 1946 weight of vinyl chloride and up to 30 per cent 01! 2428978 'gg; 1947 another polymerizable monomer compatible 2451085 Hester Oct 12 1948 therewith, and from 5 to 60 per cent by weight 10 2482706 Day Sept 1949 of the polymer of a thiaalkyl phenylphenoxyacetate wherein the thiaalkyl group has a total OTHER REFERENCES of from four to twelve sulfur and carbon atoms. s o. 367,292, Berg et al. (A. P. 0.), pub- JOACHIM DAZZI- lished Apr. 20, 1943.

REFERENCES CITED 15 The following references are of record in the file of this patent: 

1. A RESINOUS COMPOSITION OF MATTER, WHICH COMPRISES A POLYMER OF AT LEAST 70 PERCENT BY WEIGHT OF VINYL CHLORIDE AND UP TO 30 PERCENT OF ANOTHER POLYMERIZABLE MONOMER COMPATIBLE THEREWITH, AND A COMPOUND HAVING THE STRUCTURAL FORMULA: 